Continuous process for the preparation of polytrimethylene ether glycol

ABSTRACT

The invention is a continuous process for the preparation of polytrimethylene ether glycol from 1,3-propanediol reactant. In addition, the invention is directed to a continuous multi-stage process comprising reacting at least one reactant in a liquid phase in an up-flow column reactor, and forming a gas or vapor phase by-product wherein the gas or vapor phase by-product is continuously removed at the top and at least one intermediate stage.

[0001] PRIORITY

[0002] This application claims priority from U.S. provisional patentapplication Ser. No. 60/172,126, filed Dec. 17, 1999, which isincorporated herein by reference.

FIELD OF THE INVENTION

[0003] This invention concerns a process and reactor for the preparationof polytrimethylene ether glycol from 1,3-propanediol reactant. Inaddition, the invention is directed to a continuous multi-stage processin an up-flow column reactor involving forming a gas or vapor phaseby-product.

TECHNICAL BACKGROUND OF THE INVENTION

[0004] Known polyalkylene ether glycols include polyethylene glycol,poly-1,2-and 1,3-propylene ether glycol, polytetramethylene etherglycol, polyhexamethylene ether glycol and copolymers thereof. They havebeen used widely as lubricants or as starting materials for preparinglubricants used in the molding of rubbers and in the treatment offibers, ceramics and metals. They have also been used as startingmaterials for preparing cosmetics and medicines, as starting materialsor additives for water-based paints, paper coatings, adhesives,cellophane, printing inks, abrasives and surfactants and as startingmaterials for preparing resins, such as alkyd resins. They have alsobeen used as soft, flexible segments in the preparation of copolymersand segmented copolymers such as polyurethanes, thermoplastic polyestersand unsaturated polyester resins. Examples of commercially importantpolyether glycols include polyethylene glycol, poly(1,2-propyleneglycol), ethylene oxide/propylene oxide copolyols, andpolytetramethylene ether glycol.

[0005] Among the polyether glycols, the most widely used polyetherglycol is poly(1,2-propylene glycol) (PPG) because of its low cost. Thispolymer is non-crystalline, liquid at room temperature and hence easy tohandle. However, PPG has secondary hydroxyl end groups and it containshigh percentages of terminal unsaturation.

[0006] Polyoxytrimethylene glycol or polytrimethylene ether glycol orpoly(1,3-propylene glycol) can be derived either from 1,3-propanediol orfrom oxetane. These polytrimethylene ether glycols have primary hydroxylgroups and have low melting points and are highly flexible.

[0007] U.S. Pat. No. 2,520,733, which is incorporated herein byreference, discloses polymers and copolymers of trimethylene glycol anda process for the preparation of these polymers from trimethylene glycolin the presence of a dehydration catalyst such as iodine, inorganicacids (e.g., sulfuric acid) and organic acids. The trimethylene glycolderived polymers disclosed in this patent are dark brown or black incolor. The color can be improved to a light yellow color by treatmentprocesses disclosed therein. Polymers of molecular weight from about 100to about 10,000 are mentioned; however, there is a preference formolecular weights of 200-1,500 and the highest molecular weight shown inthe examples is 1096.

[0008] U.S. Pat. No. 3,326,985, which is incorporated herein byreference, discloses a process for forming a polytrimethylene glycolhaving an average molecular weight of 1,200-1,400. First,polytrimethylene glycol which has an average molecular weight of about900 is formed using hydriodic acid. This is followed by an aftertreatment which comprises vacuum stripping the polyglycol at atemperature in the range of 220-240° C. and at a pressure of 1-8 mm Hgin a current of nitrogen from 1-6 hours. The product is stated to beuseful in preparing polyurethane elastomers. There is also presented acomparative example directed to producing polytrimethylene glycol with amolecular weight of 1,500.

[0009] U.S. Pat. No. 5,403,912, which is incorporated herein byreference, disclosed a process for the polymerization of polyhydroxycompounds, including alkanediols having from 2-20 carbon atoms, in thepresence of an acid resin catalyst at temperatures of from 130-220° C.Molecular weights of from 150 to 10,000 are mentioned. A copolymer of1,10-decanediol and 1,3-propanediol having a number average molecularweight of 2050 was exemplified.

[0010] Preparation of ester terminated polyethers and hydroxy terminatedpolyethers from oxetanes and or mixtures of oxetanes and oxolanes byring opening polymerization is disclosed U.S. Pat. No. 4,970,295, whichis incorporated herein by reference. The resulting polyethers are statedto have molecular weights in the range of 250-10,000, preferably500-4,000. Synthesis of polyoxytrimethylene glycols from oxetane is alsodescribed in S.V. Conjeevaram, et al., Journal of Polymer Science:Polymer Chemistry Ed., Vol. 23, pp 429-44 (1985), which is incorporatedherein by reference.

[0011] It is desirable to prepare said polyether glycol from readilyavailable materials, not, for example, from the commercially unavailableoxetane. The polytrimethylene ether glycols heretofore obtained from thepolycondensation of 1,3-propanediol are of low molecular weight, arehighly discolored and/or require long reaction times. In addition,heretofore all process for preparing polytrimethylene ether glycol from1,3-propanediol reactant have been batch processes. Therefore, acontinuous process that produces polytrimethylene ether glycol in highyield, preferably with little or no color, and desired molecular weight,has been sought.

SUMMARY OF THE INVENTION

[0012] This invention is directed to a process of makingpolytrimethylene ether glycol comprising:

[0013] (a) providing 1,3-propanediol reactant and polycondensationcatalyst; and

[0014] (b) continuously polycondensing the 1,3-propanediol reactant topolytrimethylene ether glycol.

[0015] Preferably, the polycondensing is carried out in two or morereaction stages.

[0016] The polycondensing is preferably carried out at a temperaturegreater than 150° C., more preferably greater than 160° C., and mostpreferably greater than 180° C., and is preferably carried out at atemperature less than 250° C., more preferably less than 220° C., andmost preferably less than 210° C.

[0017] The polycondensation is preferably carried out at a pressure ofless than one atmosphere, more preferably less than 500 mm Hg, and evenmore preferably less than 250 mm Hg. While still lower pressures, forexample, even as low as 1 mm Hg can be used, especially for small scaleoperation, for larger scale, pressure is at least 20 mm Hg, preferablyat least 50 mm Hg. On a commercial scale, the polycondensation pressurewill normally be between 50 and 250 mm Hg.

[0018] In one preferred embodiment, the 1,3-propanediol reactant isselected from the group consisting of 1,3-propanediol and/or dimer andtrimer of 1,3-propanediol and mixtures thereof. In another preferredembodiment, the 1,3-propanediol reactant is selected from the groupconsisting of the 1,3-propanediol or the mixture containing at least 90weight % of 1,3-propanediol. In yet another preferred embodiment, the1,3-propanediol reactant is the 1,3-propanediol.

[0019] In one preferred embodiment, the catalyst is homogeneous.Preferably, the catalyst is selected from the group consisting of aLewis Acid, a Bronsted Acid, a super acid, and mixtures thereof. Morepreferably, the catalyst is selected from the group consisting ofinorganic acids, organic sulfonic acids, heteropolyacids, and metalsalts thereof. Even more preferably the catalyst is selected from thegroup consisting of sulfuric acid, fluorosulfonic acid, phosphorus acid,p-toluenesulfonic acid, benzenesulfonic acid, phosphotungstic acid,phosphomolybdic acid, trifluoromethanesulfonic acid,1,1,2,2-tetrafluoro-ethanesulfonic acid,1,1,1,2,3,3-hexafluoropropanesulfonic acid, bismuth triflate, yttriumtriflate, ytterbium triflate, neodymium triflate, lanthanum triflate,scandium triflate and zirconium triflate. The most preferred catalyst issulfuric acid.

[0020] In another preferred embodiment, the catalyst is heterogeneous.Preferably, the catalyst is selected from the group consisting ofzeolites, fluorinated alumina, acid-treated silica, acid-treatedsilica-alumina, heteropolyacids and heteropolyacids supported onzirconia, titania, alumina and/or silica.

[0021] In a preferred embodiment, the polycondensation is carried out ina reactor equipped with a heat source located within the reactionmedium.

[0022] In one preferred embodiment, the polycondensation is carried outin an up-flow co-current column reactor and the 1,3-propanediol reactantand polytrimethylene ether glycol flow upward co-currently with the flowof gases and vapors. Preferably, the reactor has two or more stages,more preferably 3-30 stages, even more preferably 4-20 stages, and mostpreferably 8-15 stages.

[0023] In one preferred embodiment, the 1,3-propanediol reactant is fedat multiple locations to the reactor. In addition, an inert gas ispreferably added to the reactor at one or more stages. Further,preferably at least some amount of steam (water vapor) that is generatedas a by-product of the reaction is removed from the reactor at least oneintermediate stage.

[0024] In another preferred embodiment, the polycondensation is carriedout in a counter current vertical reactor wherein and the1,3-propanediol reactant and polytrimethylene ether glycol flow in amanner counter-current to the flow of gases and vapors. Preferably, thereactor has two or more stages, more preferably 3-30 stages, even morepreferably 4-20 stages, and most preferably 8-15 stages. Preferably, the1,3-propanediol reactant is fed at the top of the reactor. Even morepreferably, the 1,3-propanediol reactant is fed at multiple locations tothe reactor. In yet another preferred embodiment, the polycondensationis first carried out in at least one prepolymerizer reactor and thencontinued in a column reactor. The 1,3-propanediol reactant preferablycomprises 90 weight % or more 1,3-propanediol. Preferably, in theprepolymerizer reactor the 1,3-propanediol is polymerized with thecatalyst to a degree of polymerization of at least 5. More preferably,the 1,3-propanediol is polymerized with the catalyst to a degree ofpolymerization of at least 10 and the column reactor comprises 3-30stages. Preferably, in the at least one prepolymerizer reactor the1,3-propanediol is polymerized with the catalyst to a degree ofpolymerization of at least 20. In the most preferred embodiment, the atleast one prepolymerizer reactor the 1,3-propanediol is polymerized withthe catalyst to a degree of polymerization of 5-10. Most preferably, theat least one prepolymerizer reactor is a well-mixed tank reactor. Mostpreferably, steam generated in the at least one prepolymerizer reactoris removed and the product of the at least one prepolymerizer is fed tothe column reactor.

[0025] Preferably, an inert gas is fed to the column reactor.

[0026] This invention is also directed to a continuous multi-stageprocess comprising reacting at least one reactant in a liquid phase inan up-flow column reactor, and forming a gas or vapor phase by-productwherein the gas or vapor phase by-product is continuously removed at thetop and at least one intermediate stage. Preferably, the gas or vaporphase by-product is water.

BRIEF DESCRIPTION OF THE DRAWINGS

[0027]FIG. 1 illustrates diagrammatically a multistage reactor. Thereactor is divided into four discrete stages using barriers betweenstages, which barriers allow separate passages for vapor and liquidflows from stage to stage.

[0028]FIG. 2 illustrates diagrammatically a co-current, upflow,multistage reactor.

[0029]FIG. 3 illustrates diagrammatically a multistage reactor withmultiple feed points.

[0030]FIG. 4 illustrates diagrammatically a multi-stage column reactorwith capability for removal of vapor at an intermediate stage.

[0031]FIG. 5a illustrates an internal column section, which providespassage of liquid and vapor between stages, and a view of a barrierseparating the stages.

[0032]FIG. 5b illustrates an internal column section, which providespassage of liquid between stages, removal of vapor and addition of inertgas.

[0033]FIG. 6 illustrates diagrammatically a reactor system comprised oftwo separate reactors, one for polymerizing 1,3-propanediol to anintermediate molecular weight greater than that of the starting materialand less than that of the desired final product, for instance a degreeof polymerization of 2 to 20, preferably 5-10, and a second reactor topolymerize the intermediate to higher molecular weight.

DETAILED DESCRIPTION OF THE INVENTION

[0034] The invention is a method for manufacture of polytrimethyleneether glycol, a polyether, continuously from thedehydration/condensation polymerization of 1,3-propanediol reactantusing a polycondensation catalyst.

[0035] Herein, “1,3-propanediol reactant” means 1,3-propanediol and/oroligomers or prepolymers of 1,3-propanediol having a degree ofpolymerization of 2-9 and mixtures thereof; “oligomer” is used to referto dimer and trimer of 1,3-propanediol; and “prepolymer” is used torefer to 1,3-propanediol based compounds having a degree ofpolymerization of 4-9. Herein, when referring to “polytrimethylene etherglycol” or copolymer, reference is made to polymers or copolymers havinga Mn of 1000 or more.

[0036] Polytrimethylene ether glycol is sometimes referred to as“polyoxytrimethylene glycol” or “3G polyol”, and 1,3-propanediol issometimes referred to as “trimethylene glycol” or “3G”. For convenienceand ease of reading, 1,3-propanediol, 3G, is sometimes used to refer to1,3-propanediol, its oligomers, prepolymers or mixtures thereof indiscussing the invention in the specification (e.g., with explaining theFigures), but not in the Examples.

[0037] The process of the invention can be operated at pressures rangingfrom above atmospheric, atmospheric or below atmospheric pressure.However, to achieve a number average molecular weight of greater than1000, typically the polycondensation (or at least the later portion ofpolycondensation) is carried out at a pressure of less than oneatmosphere, preferably less than 500 mm Hg, more preferably at apressure less than 250 mm Hg. While still lower pressures, for example,even as low as 1 mm Hg can be used, especially for small scaleoperation, for larger scale, pressure is at least 20 mm Hg, preferablyat least 50 mm Hg. Most suitable pressures are in the range of 50-250 mmHg. A pressure of 100 mm Hg can be used to produce a polytrimethyleneether glycol of molecular weight greater than 1500.

[0038] Low pressure processes are described in U.S. patent applicationSer. No. ______ (Docket #CL1482), filed concurrently herewith, and theprovisional patent application No. 60/172,264, filed Dec. 17, 1999, bothof which are incorporated herein by reference.

[0039] Temperature of the process is preferably controlled to achievethe goals of the invention, that is, high yields of desired molecularweight and a minimum of color formation. Temperature range is generallygreater than 150° C. to achieve desired reaction rates, preferablygreater than 160° C., and more preferably greater than 180° C.Temperature is generally less than 250° C., preferably less than 220°C., and more preferably less than 210° C. to minimize color. If theequipment is suitable, the temperature may be increased through thecourse of the reaction.

[0040] A suitable control system can consist of simply ensuring that allmaterial experiences the same sequence of temperature and pressure as itpasses through the reactor or it may employ an automatic controlmechanism where one or more operating conditions of the reactor arecontinually adjusted to maintain a more or less constant value of somemeasured property (e.g., viscosity) of the polymer which is related tothe molecular weight.

[0041] The process of this invention is not limited by reactorconfiguration. However a successful manufacturing process forpolytrimethylene ether glycol should provide the product within adesired time and under conditions to achieve the average molecularweight for end use applications and to limit the production of undesiredchemical species that would make the product unsuitable for end useapplications or that would require costly measures to remove. Theprocess should further provide for separation of water, which isproduced as a by-product, from the polymeric product.

[0042] Numerous reactor configurations for continuous processes areknown in the chemical process industries and could be used for themanufacture of polytrimethylene glycol. The reactor can be constructedof any material sufficient to withstand corrosion when contacted withstrong acid catalysts. Glass and Hastelloy® metal alloy are preferredreactor materials. Examples of reactors useful in the process of thisinvention include the following:

[0043] (1) Single vessels with a substantial degree of back-mixing, withor without mechanical agitation, such that the dwell time within thevessel of an identified portion of entering material is more or lessrandom. The vessel should include a heater to convert the waterby-product into steam, a control of liquid level such that awell-defined vapor space was maintained, and a point of exit of thevapor separate from the point of exit of the liquid.

[0044] (2) Sequences of back-mixed vessels, with the reaction mixturefrom one vessel continuously or intermittently constituting the feed forthe next. The steam by-product may also be conveyed from each vessel tothe next or may be discharged to a separate receptacle.

[0045] (3) Combinations of vessels which continuously exchange materialwith one another at a rate which is high enough relative to the mainflow of material into and out of the combination of vessels that thecombination acts as a single fully-back-mixed or partially-back-mixedvessel.

[0046] (4) Horizontal or vertical vessels of large ratio of length tocross-sectional linear dimension (i.e., pipes and columns) through whichthe reacting material flows and in which identified portions of thematerial pass any point along the length in approximately the same orderas at any other point (commonly known as “plug flow”). Heat should besupplied along the length to conduct the polycondensation and to convertthe water by-product into steam. The steam may flow in the samedirection (“co-current”) as the reaction mixture or in the oppositedirection (“counter-current”). At one end or the other or at someintermediate point in the vessel a point of vapor release must beprovided, where vapor can leave and carry only a negligible amount ofliquid with itself. The pipe or column may be provided with one or morepartial barriers which allow passage of the liquid and steam in thedesired directions but which largely prevent back-flow of liquid.

[0047] (5) Combinations of back-mixed vessels and pipes or columns,generally in sequence.

[0048] (6) Vessels incorporating large vertical surfaces, down which thereaction mixture flows and reacts.

[0049] (7) Vessels incorporating large moving horizontal surfaces, onwhich the reacting material is conveyed and reacts.

[0050] (8) Hybrid batch-continuous systems where part of the process iscarried out in each mode. Typically the feed material is prepared inbatches and fed continuously to a continuous reactor, or the product ofthe continuous reactor is further processed as individual batches.

[0051] In the process of this invention, the monomer, along with anyoptional comonomers (as discussed below) is fed to the reactor. Thecondensate water, any unreacted monomer and any volatile by-products arevaporized and exit from the reactor for optional subsequent separationand recycle of reactive components. The unreacted monomers or lowmolecular weight oligomers are preferably recycled back to the reactor,continuously, for the sake of process economics and environmentalconcerns.

[0052] While a number of different reactor configurations can be usedfor the continuous process of the present invention, preferably thereactor is a column reactor, more preferably a vertical column reactor.By vertical, it is meant substantially vertical, in that there can betilt or angle to the reactor.

[0053] Both co-current flow and counter-current flow reactors are usefulin the process of this invention. A co-current reactor may be furtherdescribed as an up-flow co-current reactor, which means monomer entersthe bottom of the reactor and product is removed from the top. Countercurrent reactors are also useful, wherein monomer enters at the top andproduct is removed from the bottom of the reactor. In one embodiment,the reactor is an up-flow, co-current reactor.

[0054] Column reactors useful in this invention can either be in singlestage or multiple stage configuration. Preferably the column reactor hasmultiple stages, for example, provided by means of partial barriers, inwhich the reaction mixture (monomer, oligomers, polymer, dissolvedwater) flow in one direction. If the reactor is cocurrent, the vapors(water, inert gas vaporized monomer) flow in the same direction, alsowithout flow reversal. If the reactor is countercurrent, the barrier aredesigned to allow vapor and liquid to flow in opposite directionswithout mutual interference. In all cases, separation of steam andreaction mixture take place at the top of the reactor.

[0055] While the process of this reaction can be performed in a singlestage continuous reactor, preferably, there are at least two stages,more preferably 3 or more stages, still more preferably 4 or morestages, and most preferred 8 or more stage. Preferably, there are up to30 stages, still more preferably up to 20 stages, and most preferably upto 15 stages.

[0056] The column type of reactor has the advantages of

[0057] (1) low back-flow of reaction mixture from stage to stage usingstandard engineering methods to specify the open area of the partialbarriers,

[0058] (2) opportunity in the upper stages for the re-condensation ofmonomer that becomes vaporized in the lower stages where itsconcentration is high,

[0059] (3) good agitation in all stages above the lowest, due to thepassage of steam bubbles generated below,

[0060] (4) removal of volatile impurities by steam stripping,

[0061] (5) effective use of injected nitrogen, which is forced to passthrough all stages above the place where it is injected, and

[0062] (6) ease of installation of stationary solid heterogeneouscatalyst.

[0063] A key to the present invention is that efficient heat transferfrom the column to the reactant(s) takes place. This can be accomplishedby designing the column wall configuration or by placing good heattransfer materials such as glass beads of optimum surface to volumeratio, in each stage of the column. Alternatively this can beaccomplished by providing a heat source located within the reactionmedium. The heat source is preferably an internal replaceable heatsource, preferably with non-fluid heating media. By replaceable, it ismeant that the heat source can be replaced without the need to shut downthe equipment to remove if a heater burns out. For example, there can bean internal heater located centrally to the column reactor. Other heatsources useful for this invention are well known.

[0064] As stated previously, preferably the process is operated at lessthan one atmosphere pressure. Sub-atmospheric pressure facilitatesremoval of the by-product water from the reaction mixture and alsofacilitates the removal of volatile impurities. To assist in removingwater from the mixture, an inert gas (i.e., a gas which does not reactwith or appreciably dissolve in the reaction mixture, e.g., nitrogen)may be injected into the vessel at some point along its length. Tofurther assist in removing water from the reaction mixture, anintermediate point of steam removal may be provided along the length ofthe vessel.

[0065] In the attached Figures, the catalysts are shown as rectangularboxes for simplicity. This is used to indicate that catalyst is presentin the stage depicted, and the catalyst form, shape, size, etc., willvary.

[0066] A countercurrent embodiment of the invention is diagrammaticallyillustrated in FIG. 1. FIG. 1 illustrates the optional placement ofsolid supported catalyst (9) in each of four reaction stages (8). In thepresence of the solid supported catalyst, monomer is introduced at (1).In the absence of the solid supported catalyst, 1,3-propanediol andcatalyst are introduced to the first stage of the reactor eitherseparately (catalyst introduced at (2)) or with the catalyst premixedwith the 1,3-propane diol stream (1). The process stream moves downthrough the stages which are separated by barriers (3). The barriers aredesigned such that the reaction mixture flows downwardly while volatilesare allowed to flow upwardly, ultimately exiting the reactor at (4).Polytrimethylene ether glycol product exits the column at (5).Temperature may be uniform throughout the column, or may differ atdifferent stages, for instance at (6) and (7).

[0067] An upflow reactor embodiment is presented in FIG. 2. Theembodiment of FIG. 2 again illustrates the optional placement of solidsupported catalyst (9) in each of four reaction stages (8). In thepresence of the solid supported catalyst, monomer is introduced at (1).In the absence of the solid supported catalyst, 1,3-propanediol andcatalyst are introduced to the first stage of the reactor eitherseparately (catalyst introduced at (2)) or with the catalyst premixedwith the 1,3-propane diol stream (1). The process stream moves upthrough the stages which are separated by barriers (3). These barriersare designed such that the reaction mixture flows upwardly whilevolatiles are also allowed to flow upwardly, ultimately exiting thereactor at (4). Polytrimethylene ether glycol product exits the columnat (5). Temperature may be uniform throughout the column, or may differat different stages, for instance at (6) and (7).

[0068] A multi-feed reactor embodiment is presented in FIG. 3. FIG. 3also illustrates the optional placement of solid supported catalyst (9)in each of four reaction stages (8). In the presence of the solidsupported catalyst, monomer is introduced at individual feed points (1)corresponding to some or all of the reactor stages. In the absence ofthe solid supported catalyst, 1,3-propanediol and catalyst areintroduced to each stage of the reactor either separately or with thecatalyst premixed with the 1,3-propane diol stream at one or more ofeach (1) feed point. The process stream moves down through the stageswhich are separated by barriers (3). The barriers are designed such thatthe reaction mixture flows downwardly while volatiles are allowed toflow upwardly, ultimately exiting the reactor at (4). Polytrimethyleneether glycol product exits the column at (5). Temperature may be uniformthroughout the column, or may differ at different stages, for instanceat (6) and (7).

[0069]FIG. 4 illustrates diagrammatically a multi-stage co-current,up-flow column reactor with the capability to remove steam, which is thecondensate water vapor generated as a product of the reaction, at aparticular point. As there may also be monomer present in the lowerreaction stages, this step is preferred not to take place in thosestages. In this figure, monomer, 1,3-propanediol is added at the bottom(20) of the reactor. A side-stream comprised of water vapor is removedat (21), which combines with water from the top of the reactor (22) forsubsequent treatment (23). A valve (24) can be used to control theremoval of the water vapor. Further illustrated in this figure isaddition of an inert gas at (25), to the reactor beyond where water wasremoved. The inert gas can be any gas that is chemically inert and notsubstantially soluble in the reaction medium. Nitrogen is the preferredinert gas. Polymer product exits the reactor at (26).

[0070]FIG. 5a illustrates a view of an internal section of the reactorof FIG. 4. The liquid level fills the reactor stage at (30) and thereaction mixture plus gas and vapors pass through openings (32) in thebarrier (31) between the stages. A side opening (34) in the barrier (31)allows for introduction of inert gas. A centrally located heater (33) isshown. The overhead view of a barrier (31) shows a large central opening(35) for the heater and three additional openings (32) through which thereaction mixture plus gas and vapors pass.

[0071]FIG. 5b illustrates an alternative internal section of the reactorof FIG. 4. In this section, there is a liquid level (40) and a vaporspace (46). A dipleg (47) drops from an upper stage (48) to below theliquid level (40) in a lower stage (49) to create a path forsubstantially liquid from the reaction mixture to pass from the lowerstage (49) to the upper stage (48). There is also provided an opening(50) on the side of barrier (41) to provide for removal of vapor fromthe vapor space (46). The vapor comprises water vapor and volatiles inthe reaction mixture. There is a side opening (44) in barrier (41) toallow for introduction of an inert gas. A centrally located heater (43)is shown. The overhead view of the barrier (41) shows a large centralopening (45) for the heater and one additional opening (42), which isconnected to dipleg (47) for liquid to pass from lower stage (49) toupper stage (48).

[0072]FIG. 6 illustrates an alternative embodiment wherein a large partof the reaction is carried out in a non-columnar reactor (51) comprisingone or more stages and the reaction mixture is continuously conveyedfrom this vessel into the lowest stage (52) of a multi-stage co-currentup-flow column reactor (53). Monomer, 1,3-propanediol (54) is fed intovessel (51), then fed via piping (55) into stage (52). Steam produced inthe reaction is vented from vessel (51) at (56). An inert gas is shownadded to stage (52) at (57). Polymer product is removed at (58) and thereaction vapors are vented at (59). This arrangement reserves the columnfor the final portion of the reaction where the use of multiplesequential stages is important for efficiency of reaction. For a givenrate of production the size of the column can be reduced, with much ofthe reaction being carried out in a less expensive first vessel. The twovessels may be operated under different pressures, with the first vesselbeing preferably operated at a pressure closer to atmospheric than thecolumn. The column is preferably operated under vacuum. (Thisarrangement can also be used with a column operating in thecounter-current mode.) The catalysts used in the process of the presentinvention are dehydration polycondensation catalysts. Preferredhomogeneous polycondensation catalysts are those acids with a pKa lessthan about 4, preferably with a pKa less than about 2, and includeinorganic acids, organic sulfonic acids, heteropolyacids,perfluoro-alkyl sulfonic acids and mixtures thereof. Also preferred aremetal salts of acids with a pKa less than about 4, including metalsulfonates, metal trifluoroacetates, metal triflates, and mixturesthereof including mixtures of the salts with their conjugate acids.Specific examples of catalysts include sulfuric acid, fluorosulfonicacid, phosphorous acid, p-toluenesulfonic acid, benzenesulfonic acid,phosphotungstic acid, phosphomolybdic acid, trifluoromethanesulfonicacid, 1,1,2,2-tetrafluoroethanesulfonic acid,1,1,1,2,3,3-hexafluoropropanesulfonic acid, bismuth triflate, yttriumtriflate, ytterbium triflate, neodymium triflate, lanthanum triflate,scandium triflate, zirconium triflate. A preferred catalyst is sulfuricacid, used in a concentration of from 0.1 to 5.0%, by weight of thereaction mixture. A preferred concentration range is 0.25 to 2.5%.

[0073] Suitable heterogeneous catalysts are zeolites, acid-treatedsilica, acid-treated silica-alumina, acid-treated clays, heterogeneousheteropolyacids and sulfated zirconia.

[0074] Generally, catalyst concentrations are typically about 0.1% ormore, by weight of the reaction mixture, more preferably about 0.25% ormore, and preferably used in a concentration of about 20% or less, byweight of the reaction mixture, more preferably 10% or less, even morepreferably 5% of less, and most preferably 2.5% or less. Catalystconcentrations can be as high as 20 weight % for heterogeneous catalystsand lower than 5 weight % for soluble catalysts.

[0075] Catalyst precursors may also be employed. For example,1,3-dibromo-propane yields, after reaction with 1,3-propanediol,hydrogen bromide which then functions as a dehydration catalyst. Similarresults are obtained with 1,3-diiodo-propane and other dihaloalkanes.

[0076] The process of the present invention will providepolytrimethylene ether glycol continuously with improvement inpolymerization rate and polymer color.

[0077] The starting material for the present process can be any1,3-propanediol reactant or a mixture thereof. The quality of thestarting material is important for producing high quality polymer. The1,3-propanediol employed in the process of the present invention may beobtained by any of the various chemical routes or by biochemicaltransformation routes. Preferred routes are described in U.S. Pat. Nos.5,015,789, 5,276,201, 5,284,979, 5,334,778, 5,364,984, 5,364,987,5,633,362, 5,686,276, 5,821,092, 5,962,745 and 6,140,543, U.S. patentapplication Ser. Nos. 09/346,418, 09/382,970, 09/382,998 and 09/505,785,and WO 98/57913, 00/10953 and WO 00/14041, all of which are incorporatedherein by reference. Preferably the 1,3-propanediol has a purity ofgreater than 99%. The 1,3-propanediol-based starting materials may bepurified prior to use, for example by treatment with an acid catalyst atan elevated temperature and reaction time to react impurities into formsthat can be separated as described in WO 00/10953, which is incorporatedherein by reference.

[0078] In some instance, it may be desirable to use up to 10% or more oflow molecular weight oligomers where they are available. Thus,preferably the starting material consists essentially of 1,3-propanedioldiol and dimer and trimer thereof. The most preferred starting materialis comprised of 90 weight % or more 1,3-propanediol, more preferably 99weight % or more.

[0079] The starting material for the present process can contain up to50% by weight (preferably 20 weight % or less) of comonomer diols inaddition to the 1,3-propanediol and/or its oligomers. Comonomer diolsthat are suitable for use in the process include aliphatic diols, forexample 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol,1,10-decanediol, 1,12-dodecanediol,3,3,4,4,5,5-hexafluro-1,5-pentanediol,2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-hexadecafluoro-1,12-dodecanediol,cycloaliphatic diols, for example 1,4-cyclohexanediol,1,4-cyclohexanedimethanol and isosorbide, polyhydroxy compounds, forexample glycerol, trimethylolpropane, and pentaerythritol. A preferredgroup of comonomer diol is selected from the group consisting of2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol,2,2-diethyl-1,3-propanediol, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol,1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, isosorbide, andmixtures thereof. Thermal stabilizers, antioxidants and coloringmaterials may be added to the polymerization mixture or to the finalpolymer if necessary.

[0080] There is also provided in this invention a continuous processcomprising a continuous multi-stage process comprising in an up-flowcolumn reactor, providing as reactant or product a liquid phase and agas or vapor phase to the reactor wherein the gas or vapor phase iscontinuously removed at the top and at least one intermediate stage.Preferably the process is a condensation process wherein the processforms a gas or vaporous product by condensing one or more of thereactants. An example of such a reaction is a dehydration reactionwherein water vapor is generated, for example in the reactant of1,3-propanediol to produce polytrimethylene ether glycol and water.

[0081] The process of this invention provides a high purity, highmolecular weight polymer of polytrimethylene ether glycol having anumber average molecular weight of at least 1,000, more preferably atleast 1,500, even more preferably at least 1,650 and most preferably atleast 2,000. Similarly the molecular weight is less than 5,000 (e.g.,4,950 or less), preferably less than 4,000, and more preferably lessthan 3,500. The polymer after purification has essentially no acid endgroups. For a polymer having a number average molecular weight of 2,350,the hydroxyl number (ASTM E222 method) is 47.5.

[0082] Advantageously, the polymer has an APHA (prior to any postpurification) (ASTM D1209) color of less than 120, preferably less than100 and more preferably less than 50. There is also an OCE (oligomers ofcyclic ethers) content (prior to any post purification) of less than 2%,preferably less than 1%.

[0083] The polyether glycol prepared by the process of the presentinvention can be purified further to remove the acid present by meansknown in the art. It should be recognized that in certain applicationsthe product may be used without further purification. However, thepurification process improves the polymer quality and functionalitysignificantly and it is comprised of (1) a hydrolysis step to hydrolyzethe acid esters that are formed during the polymerization and (2)typically (a) water extraction steps to remove the acid, unreactedmonomer, low molecular weight linear oligomers and oligomers of cyclicethers (OCE), (b) a solid base treatment to neutralize the residual acidpresent and (c) drying and filtration of the polymer to remove theresidual water and solids.

[0084] The invention is a low cost, rate efficient continuous way toproduce 3G polyol or improved quality. It is particularly advantageousfor producing 3G polyol with a desired molecular weight and low color.

[0085] The invention is demonstrated in the following examples, whichare not intended to be limiting, wherein all parts, percentages and thelike are by weight, unless indicated otherwise.

EXAMPLES Example 1 Dehydration of 1,3-propanediol in a Single StageColumn

[0086] In this example the flow-through reactive column used was asingle stage Vigreux distilling glass column with a column length of 600mm and 24/40 ground glass joints. It was obtained from Lab Glass Inc.,Vineland, N.J. (Model No. LG-5890).

[0087] The glass column reactor sets atop a round-bottom flask and wasequipped with a distillation head with a Liebig take-off condenser whichwas cooled by running water at ambient temperature. The condenser wasfitted with a graduated fraction cutter and a distillate receiver. TheVigreux column was heated by wrapping with heater tape; it was insulatedand maintained at 200° C. and above. A hot oil condenser maintained at110° C. was utilized at between the top of the column and thedistillation head to condense and recycle back any 3G vaporized in thecolumn during the polymerization.

[0088] 3G monomer with dissolved catalyst was introduced at the top ofthe Vigreux column, through a liquid injection pump, such as ISCOLC-5000 syringe pump, (ISCO, Inc., Lincoln, Nebr.) having a range ofinjection rate between 1.5 to 400 mL per hour. The polymerization tookplace in the multi-manifolds of the column, which was maintained atelevated temperature, in this example 200° C. and above. Regulatednitrogen was introduced in the bottom of the column. (Estimated rate: 25ml/minute) The 3G polyol polymer product of the reaction was collectedin the round-bottom flask which was optionally immersed in a water bathfor temperature control.

[0089] The first example of continuous 3G polyol polymerization in thebench scale glass reactive column pilot reactor (run 1) demonstrated thecontrol of the reactor stability and that dehydration of the monomer viaetherification occurred with minimum degradation. The residence time inthis single stage column (with essentially plug flow) was 45 seconds. At1.3 ml/minute injection rate at 200° C., with 1% sulfuric acid ascatalysts, a 2% yield was obtained, based on the amount of watercondensate collected. The condensate was almost pure water (asdemonstrated by refractive index) and the color of both the watercondensate and the product liquid was water clear.

[0090] The results of run 1 and runs 2-4 at higher temperatures and/orlonger retention times are shown in Table 1. Increasing the apparentcolumn temperature from 200 to 220° C. (actual reaction temperature:from 190 to 210° C.), led to a 300+% improvement in calculated yield.The calculated yield, based on the amount of water condensate, increasedfrom 2.1% to 7.1%. The condensate was again essentially pure water. Boththe condensate and the polymer liquid were water clear. There were nosigns of degradation. The apparent activation energy for thepolycondensation was estimated to be about 20 KCal/mole. TABLE 1 3GContinuous Polymerization in a Vigreux Column Feed Column Residence RunFeed Rate Temp. Condensate Time Number Material (mL/min) (° C.) Mass (g)R.I.* Yield (min) 1 3G + H₂SO₄ (1%) 1.24 200 0.90 1.3400 2.1% 0.75 23G + H₂SO₄ (1%) 1.20 212 2.21 1.3397 6.0% 1.13 3 3G + H₂SO₄ (1%) 1.08217 2.60 1.3394 8.0% 1.00 4 3G + H₂SO₄ (1%) 0.99 216 3.24 1.3423 10.9%1.17

Example 2 Dehydration of 1,3-propanediol in a Glass Bead Packed Column

[0091] The column of Example 1 was modified to increase the number ofstages and to lengthen the residence time (and mixing) and to increasethe yield. This example demonstrated the 3G continuous polymerization ina glass column reactor similar to that of Example 1, except that asingle stage conventional distillation column packed with glass beadswas used instead of the Vigreux column.

[0092] The column used in this example was a Hempel type distillationcolumn of 500 mm in length and with 24/40 ground glass joints. (LabGlass Inc, Vineland, N.J., Model No. LG-5820.) It is plain tube with asealed-in glass honeycomb support for packing near the bottom. Thecolumn was packed with glass beads of 5 mm diameter (Lab Glass Inc.,Model No. LG-6750-104).

[0093] In all other respects, the polymerization reactor was identicalto that in Example 1. The residence time of 3G in the column under theseconditions was about 1.5 minutes. Results of the 3G continuouspolymerization are summarized in Table 2. As in Example 1, yield wascalculated from the amount of water condensate collected.Characterization of the product from run 6 is included in Table 6. TABLE2 3G Continuous Polymerization in a Glass Bead Packed Column Feed ColumnResidence Run Feed Rate Temp. Condensate Time Number Material (mL/min)(° C.) Mass (g) R.I.^((a)) Yield (min) 5 3G + H₂SO₄ (1%) 1.32 200 6.431.3365 16.2% 1.42 6 3G + H₂SO₄ (1%) 1.32 208 10.10 1.3383 25.5% 1.25 73G + H₂SO₄ (1%) 1.20 219 7.71 1.3395 21.4% 1.72 8 3G + H₂SO₄ (1%) 1.13214 7.16 1.3388 21.1% 1.72 9 3G + H₂SO₄ (1%) 1.13 208 7.00 1.3385 20.7%1.93

Example 3 Dehydration of 1,3-propanediol in a Single Stage Glass BeadPacked Column with Multiple Passes

[0094] The conditions of Example 2 (bead packed column) were repeated tosimulate a multi staged reactor. After a complete passing of thereaction mixture through the column as in Example 2, the collectedeffluent from the round bottom flask was passed through the columnrepeatedly. Run number 10 was thus a single pass experiment similar toruns 5-9 above. Run number 11 uses the product of run 10 as feedmaterial. Run number 14 below, then, was the result of 5 passes throughthe single pass column simulating a 5 stage reactor. Yield wascalculated from the amount of water condensate collected.Characterization of the products from run numbers 12, 13 and 14 isincluded in Table 6. TABLE 4 3G Polyol Continuous Polymerization -Single Stage Column/Multi-Pass Experiment^((a)) Polymerization FeedColumn Condensate Residence Run Feed Rate Temp Mass Accumulative TimeNumber Material (mL/min) (° C.) (g) Yield (min) 10 3G + H₂SO₄ (1%) 1.07210 4.36 10.9% 1.63 11 Run 10 Product 1.06 211 5.07 23.5% 1.33 12 Run 11Product 1.12 210 4.98 35.9% 1.53 13 Run 12 Product 1.08 212 4.60 47.4%1.40 14 Run 13 Product 0.99 216 1.87 52.0% 1.28

Example 4 Dehydration of 1,3-propanediol in a Multi Stage Column

[0095] The apparatus of example 1 was modified. The Vigreaux column wasreplaced with a an Oldershaw perforated bubble plate distilling columnwith 20 stages. (Model no. LG-5621, Lab Glass Inc., Vineland, N.J.).Conditions for runs number 15-18 are presented in Table 5. Yield wascalculated from the amount of water condensate collected.Characterization of the product from run number 15 is included in Table6. Table 7, below compares the results of two batch experiments, not ofthe invention, to continuous runs number 15, 17 and 18. TABLE 5 3GPolyol Continuous Polymerization-Multi-Stage Column Experiment^((a))Polymerization Feed Set Condensate Residence Run Feed Rate Temp. MassTime Number Material (mL/min) (° C.) (g) Yield (min) 15 3G + H₂SO₄ 1.12210 15.66 46.9% 12.00 (1%) 16 3G + H₂SO₄ 0.98 210 18.37 63.0% 12.45 (1%)17 3G + H₂SO₄ 1.06 210 30.37 96.3% 11.13 (2.5%) 18 3G + H₂SO₄ 1.06 21037.98  109% 10.00 (4.0%)

[0096] TABLE 6 Molecular Weight^((a)) of 3G Polyol Produced fromContinuous Polymerization in a Column Reactor MW_(i) Sample - Run #6Sample - Run #12 Sample - Run #13 Sample - Run #14 Sample Run #15Oligomer n g/mol n_(i) (%)^((b)) n_(i) * MW₁ n_(i) (%)^((b)) n_(i) *MW_(i) n_(i) (%)^((b)) n_(i) * MW_(i) n_(i) (%)^((b)) n_(i) * MW_(i)n_(i) (%)^((b)) n_(i) * MW_(i) 3G — 76.095 60.600 46.114 42.000 31.96023.900 18.187 15.200 11.566 27.800 21.154 Dimer 2 134.175 17.400 23.34625.500 34.215 24.400 32.739 22.000 29.519 24.000 32.202 Trimer 3 192.2554.440 8.536 10.200 19.610 14.100 27.108 15.200 29.223 12.800 24.609Tetramer 4 250.335 1.790 4.481 4.160 10.414 7.960 19.927 9.500 23.7826.610 16.547 Pentamer 5 308.415 0.724 2.233 1.660 5.120 4.060 12.5225.200 16.038 3.240 9.993 Hexamer 6 366.495 0.401 1.470 0.752 2.756 1.9907.293 2.910 10.665 1.720 6.304 Heptamer 7 424.575 0.320 1.359 0.3931.669 1.070 4.543 1.580 6.708 1.110 4.713 Octamer 8 482.655 0.150 0.7240.160 0.772 0.410 1.979 0.700 3.379 0.500 2.413 Sum w/o 3G 25.225 42.14942.825 74.555 53.990 106.110 57.090 119.313 49.980 Sum w/3G 85.82588.262 84.825 106.515 77.890 124.297 72.290 130.879 77.780 117.935 Mnw/o 3G (g/mol) 167.091 174.093 196.537 208.990 193.638 Mn w/3G (g/mol)102.840 125.570 159.580 181.047 151.626

[0097] TABLE 7 3G Polyol Polymerization Batch vs. Continuous ColumnProcess Polymer Polymer Catalyst^((a)) Residence Viscosity MolecularPolymerization Percentage Time (min) (cPoise) Wt. (Mn) Batch experimenta 1.0% 240.00  226.3 417^((a)) Batch experiment b 1.0% 240.00  352.3680^((a)) Continuous 1.0% 12.00  79.4 193.6^((b)), (Run no. 15)179^((a)) Continuous 2.5% 11.13 341.0 500^((a)) (Run no. 17) Continuous4.0% 10.00 599.3 690^((a)) (Run no. 18)

Example 5

[0098] 1,3-Propanediol was mixed with sufficient sulfuric acid toprovide a 10% solution of the acid in the diol. This solution wastransferred to a mixing drum and diluted with the diol to provide a 1%solution of sulfuric acid in the diol. The solution was preheated to atemperature of 120° C.

[0099] The preheated 1% sulfuric acid/diol solution was introduced tothe bottom of a co-current upflow 15-stage continuous glass columnreactor, equipped with a central heating unit, wherein the stages wereseparated by perforated flow distribution plates (trays). Nitrogen wasintroduced at a low flow rate at the bottom of the column to provideinitial agitation.

[0100] Polymer product was discharged from the side of the columnreactor near the top, and collected. Water and water vapor were sweptfrom the top of the column, condensed, and collected. Results arepresented below in Table 8 for several runs, 1-4, under theseconditions.

Example 6

[0101] Example 5 was repeated except that the column was divided into 8reaction stage, with the temperature in stages 1 and 2 at 175° C.,temperature in stages 3-5 was 190° C., and temperature in stages 6-8 was180° C. The polymer production rate was 0.8 kg/hr. Vacuum was appliedand the absolute pressure was 100 mm Hg. In the final stage, there was asweep of nitrogen provided at a rate of 0.4 kg/hr, which reduced thesteam partial pressure in stage 8 to 33 mm Hg. Results are included asRun 5 in Table 8.

Example 7

[0102] Example 6 was repeated but with steam being substantially allwithdrawn at the top of stage 4 and nitrogen being added at the bottomof stage 5 at a rate of 0.4 kilograms per hour. The temperature of allstages was held at around 180° C. Absolute pressure at the top of thereactor was 100 mm Hg. Polymer production rate was 0.8 kg/hour. Resultsare included as Run 6 in Table 8.

Example 8

[0103] Example 7 was repeated but with the temperature of the top 4stages increased to 190° C. Results are included as Run 7 in Table 8.TABLE 8 3G Polyol Continuous Polymerization - Multi-StageColumn/Co-current Upflow Polymer- ization Polymer Column Number Run AcidRate Temp Average Number Concentration (kg/hr) (° C.) MW of polymer 1 1%H₂SO₄ 3.82 180  252 2 1% H₂SO₄ 3.05 180  546 3 1% H₂SO₄ 2.29 180  792 41% H₂SO₄ 3.82 190  852 5 1% H₂SO₄ 0.8  175, 190, 180 1680 6 1% H₂SO₄0.8  180 1801 7 1% H₂SO₄ 0.8  180,180,190 1898

[0104] As can be seen from Table 8, a range of molecular weights can beproduced by varying reaction conditions.

[0105] The run 5 polymer was purified as described below. Equal volumeof water was added to the polymer and the reaction mixture wasmaintained at 100° C. for 6 hours and a stirring speed of 180 rpm undera nitrogen atmosphere. After 6 hours, the heater and the stirrer wereturned off and the mixture was allowed to phase separate. The topaqueous phase was decanted and the polyether phase was washed furtherwith distilled water three more times to extract out most of the acidand the oligomers. The residual acid left in the polyether glycol wasneutralized with calcium hydroxide in excess. The polymer was dried at100° C. under reduced pressure for 2-3 hours and then the dried polymerwas filtered hot through a Whatman filter paper precoated with a Celitefilter aid. The number average molecular weight determined from NMR wasfound to be 2,140.

[0106] The foregoing disclosure of embodiments of the present inventionhas been presented for purposes of illustration and description. It isnot intended to be exhaustive or to limit the invention to the preciseforms disclosed. Many variations and modifications of the embodimentsdescribed herein will be evident to one of ordinary skill in the art inlight of the above disclosure.

1. A process of making polytrimethylene ether glycol comprising: (a)providing 1,3-propanediol reactant and polycondensation catalyst; and(b) continuously polycondensing the 1,3-propanediol reactant topolytrimethylene ether glycol.
 2. The process of claim 1 wherein thepolycondensing is carried out in two or more reaction stages.
 3. Theprocess of claim 1 wherein the polycondensing is carried out at atemperature greater than 150° C.
 4. The process of claim 3 wherein thetemperature is greater than 160° C.
 5. The process of claim 4 whereinthe temperature is greater than 180° C.
 6. The process of claim 1wherein the polycondensing is carried out at a temperature less than250° C.
 7. The process of claim 6 wherein the temperature is less than220° C.
 8. The process of claim 7 wherein the temperature is less than210° C.
 9. The process of claim 3 wherein the temperature is less than210° C.
 10. The process of claim 1 wherein the polycondensation iscarried out at a pressure of less than one atmosphere.
 11. The processof claim 10 wherein the pressure is less than 500 mm Hg.
 12. The processof claim 11 wherein the pressure is less than 250 mm Hg.
 13. The processof claim 11 wherein the pressure is greater than 1 mm Hg
 14. The processof claim 12 wherein the pressure is greater than 20 mm Hg.
 15. Theprocess of claim 14 wherein the pressure is greater than 50 mm Hg. 16.The process of claim 1 wherein the 1,3-propanediol reactant is selectedfrom the group consisting of 1,3-propanediol and/or dimer and trimer of1,3-propanediol and mixtures thereof.
 17. The process of claim 16wherein the 1,3-propanediol reactant is selected from the groupconsisting of the 1,3-propanediol or the mixture containing at least 90weight % of 1,3-propanediol.
 18. The process of claim 16 wherein the1,3-propanediol reactant is the 1,3-propanediol.
 19. The process ofclaim 17 wherein the polycondensation pressure is between 50 and 250 mmHg.
 20. The process of claim 1 wherein the catalyst is homogeneous. 21.The process of claim 20 wherein the catalyst is selected from the groupconsisting of a Lewis Acid, a Bronsted Acid, a super acid, and mixturesthereof.
 22. The process of claim 21 wherein the catalyst is selectedfrom the group consisting of inorganic acids, organic sulfonic acids,heteropolyacids, and metal salts thereof.
 23. The process of claim 1wherein the catalyst is selected from the group consisting of sulfuricacid, fluorosulfonic acid, phosphorus acid, p-toluenesulfonic acid,benzenesulfonic acid, phosphotungstic acid, phosphomolybdic acid,trifluoromethanesulfonic acid, 1,1,2,2-tetrafluoro-ethanesulfonic acid,1,1,1,2,3,3-hexafluoropropanesulfonic acid, bismuth triflate, yttriumtriflate, ytterbium triflate, neodymium triflate, lanthanum triflate,scandium triflate and zirconium triflate.
 24. The process of claim 1wherein the catalyst is sulfuric acid.
 25. The process of claim 1wherein the catalyst is heterogeneous.
 26. The process of claim 25wherein the catalyst is selected from the group consisting of zeolites,fluorinated alumina, acid-treated silica, acid-treated silica-alumina,heteropolyacids and heteropolyacids supported on zirconia, titania,alumina and/or silica.
 27. The process of claim 1 wherein thepolycondensation is carried out in a reactor equipped with a heat sourcelocated within the reaction medium.
 28. The process of claim 1 whereinthe polycondensation is carried out in an up-flow co-current columnreactor and the 1,3-propanediol reactant and polytrimethylene etherglycol flow upward co-currently with the flow of gases and vapors. 29.The process of claim 28 wherein the reactor has two or more stages. 30.The process of claim 28 wherein the reactor has 3-30 stages.
 31. Theprocess of claim 28 wherein the reactor has 4-20 stages.
 32. The processof claim 28 wherein the reactor has 8-15 stages.
 33. The process ofclaim 30 wherein the 1,3-propanediol reactant is fed at multiplelocations to the reactor.
 34. The process of 30 wherein an inert gas isadded to the reactor at one or more stages.
 35. The process of claim 30wherein at least some amount of steam (water vapor) that is generated asa by-product of the reaction is removed from the reactor at least oneintermediate stage.
 36. The process of claim 1 wherein thepolycondensation is carried out in a counter current vertical reactorwherein and the 1,3-propanediol reactant and polytrimethylene etherglycol flow in a manner counter-current to the flow of gases and vapors.37. The process of claim 36 wherein the reactor has two or more stages.38. The process of claim 37 wherein the 1,3-propanediol reactant is fedat the top of the reactor.
 39. The process of claim 33 wherein the1,3-propanediol reactant is fed at multiple locations to the reactor.40. The process of claim 1 wherein the polycondensation is first carriedout in at least one prepolymerizer reactor and then continued in acolumn reactor, the 1,3-propanediol reactant comprises 90 weight % ormore 1,3-propanediol, and in the prepolymerizer reactor the1,3-propanediol is polymerized with the catalyst to a degree ofpolymerization of at least
 5. 41. The process of claim 40 wherein in theat least one prepolymerizer reactor the 1,3-propanediol is polymerizedwith the catalyst to a degree of polymerization of at least 10 and thecolumn reactor comprises 3-30 stages.
 42. The process of claim 40wherein in the at least one prepolymerizer reactor the 1,3-propanediolis polymerized with the catalyst to a degree of polymerization of atleast
 20. 43. The process of claim 41 wherein the at least oneprepolymerizer reactor is a well-mixed tank reactor.
 44. The process ofclaim 41 wherein steam generated in the at least one prepolymerizerreactor is removed and the product of the at least one prepolymerizer isfed to the column reactor.
 45. The process of claim 44 wherein an inertgas is fed to the column reactor.
 46. A continuous multi-stage processcomprising reacting at least one reactant in a liquid phase in anup-flow column reactor, and forming a gas or vapor phase by-productwherein the gas or vapor phase by-product is continuously removed at thetop and at least one intermediate stage.